Conjugated microporous macromolecule catalyst complexed with cobalt, chromium, zinc, copper or aluminium, preparation and use thereof

ABSTRACT

Disclosed are a type of catalyst which can catalyse the ring-addition reaction of CO 2  and an alkylene oxide at 0˜180° C. under 0.1˜8.0 MPa to produce a corresponding cyclic carbonate, and the preparation thereof. The catalyst is a conjugated microporous macromolecule polymer complexed with cobalt, chromium, zinc, copper or aluminium, and by using the macromolecule catalysts complexed with different metals to catalyse the reaction of CO 2  and alkylene oxide at normal temperature and normal pressure, a yield of the corresponding cyclic carbonate of 35%˜90% can be obtained. The catalyst is easy to recover and the re-use of the catalyst has no influence on the yield; additionally, the yield can reach over 90% by controlling the reaction conditions.

FIELD OF THE INVENTION

In this invention, a series of new metals including Co, Cr, Zn, Cu, andAl coordinated conjugated microporous polymer catalysts were designed,synthesized, and used to catalyze the reaction of the epoxides and CO₂to produce corresponding cyclic carbonates at mild conditions.Meanwhile, the catalysts can be recycled easily and reused for severaltimes without reducing the yields, which obviously increases theutilization of catalysts.

BACKGROUND OF THE INVENTION

Carbon dioxide is one of the main greenhouse gases, but it is safe,nontoxic, inexpensive, and abundant. Since the industrial revolution,the carbon dioxide level in the atmospheric layer was rising year byyear, enhancing the greenhouse effect, which leads to the globe warmingand the frequent occurrence of the disastrous weather. Therefore, how todispose and use CO2 has attracted the attention of the whole world.Recently, through the efforts of scientists around the world, it is themain strategy to conceive efficient carbon capture or conversion viachemical technologies. One of the most promising reactions in this areais the cycloaddition reaction of CO2 and epoxides to cyclic carbonates(CCs). However, numerous reported catalyst systems suffered from theharsh operation conditions and their catalytic activities were limitedby the requirement of high pressure and temperature, together with theseparation difficulties, which lead to the low efficiency to utilizethem. Thus, the development of new effective catalytic systems forcatalytic conversion with CO2 under mild conditions is desired,especially in real world applications.

SUMMARY OF THE INVENTION

In order to achieve the desire of the catalytic conversion of carbondioxide under mild conditions, we designed and synthesized the cobalt,chromium, zinc, copper or aluminum-conjugated microporous polymercatalysts (CMP-1, CMP-2, CMP-3, CMP-4 and CMP-5, respectively) based onthe previous research. The chemical conversion of CO₂ with epoxides toform corresponding cyclic carbonates using the CMP-1˜5 catalyst systemnot only can obtain ideal effect at mild condition, but also can speedthe production of cyclic carbonate at high temperature and pressure.

Synthesis methods for the cobalt, chromium, zinc, copper oraluminum-conjugated microporous polymer catalysts:

1. Synthesis of Salen:

With Monohydric alcohol (methanol or ethanol) as a solvent, a mixturesolution of R₁-substituted salicylaldehyde and 1,2-diaminocyclohexane(mole ratio=1:1˜30) was stirred for 3˜15 hours at 0˜150° C. to affordthe Salen compounds.

2. Synthesis of Salen-Co—X (Salen-Cr—Cl, Salen-Zn, Salen-Cu):

1) Synthesis of Salen-Co—X:

Synthesis of Salen-Co: To a solution of the Salen in toluene under argonwas added a solution of Co(OAc)₂ in CH₃OH via a syringe, affording adark red reaction mixture. It was heated to 80˜100° C., stirred andrefluxed for 4˜5 hours. Then the reaction mixture was cooled down toroom temperature and concentrated, and the afforded residue wasdissolved in CH₂Cl₂ and filtered through celite. Removing solvent of thefiltrate afforded a dark red powder Salen-Co;

Synthesis of Salen-Co—X: To a solution of the Salen-Co in toluene andCH₂Cl₂ (volume ratio of toluene and CH₂Cl₂=1:3) was added CH₃COOH(HCl orHBr or HI) under argon via a syringe. The solution quickly changed fromred to brown. After stirring at 25° C. for 4˜5 hours, all solvents andexcess acid were removed at reduced pressure, affording brown powderSalen-Co—X.

2) Synthesis of Salen-Cr—Cl:

THF was added to a mixture of Salen and CrCl₂ via a syringe under argon.The reaction mixture was stirred at 25° C. for 24 hours. The reactionmixture then was stirred under air at ambient temperature for anadditional 24 hours. After the reaction mixture was poured into diethylether, the organic layer was washed with aqueous saturated NH₄Cl andbrine in turn. After filtration, the organic layer was collectedyielding a brown powder Salen-Cr—Cl.

3) Synthesis of Salen-Zn:

THF was added to a mixture of Salen and Et₂Zn via a syringe under argon.The reaction mixture was stirred at 25° C. for 24 hours. The crudeproduct was isolated from the concentrated reaction mixture by removalof the solvent under reduced pressure. A pure product Salen-Zn wasobtained after recrystallization using THF and water.

4) Synthesis of Salen-Cu:

Anhydrous ethanol was added to a mixture of Salen and Cu(OAc)₂ underargon via a syringe. The reaction mixture was stirred at 80° C. for 24hours. The solvent was removed under reduced pressure, yielding a darkgreen powder Salen-Cu.

3. Synthesis of CMP

1) Synthesis of CMP-1:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Co—X, alkynyl benzeneA (mole ratio of Salen-Co—X and alkynyl benzene A=1:2˜3), copper (I)iodide and tetrakis-(triphenylphosphine)palladium(0) under argon via asyringe. The reaction mixture was heated to 40° C. and stirred for 40min-1 hour. Then, the reaction mixture was heated to 80˜100° C. andrefluxed for 72˜96 hours. The mixture was cooled to room temperature andthe insoluble precipitated polymer was filtered and washed withdichloromethane, methanol, water, and acetone in turn. Furtherpurification of the polymer was carried out by Soxhlet extraction withmethanol and dichloromethane (volume ratio=1:1) for 24˜36 hours. Theproduct CMP-1 was dried in vacuum for 24 hours at 70° C.

2) Synthesis of CMP-2:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Cr—Cl, alkynylbenzene A (mole ratio of Salen-Cr—Cl and alkynyl benzene A=1:2˜3),copper (I) iodide and tetrakis-(triphenylphosphine)palladium(0) via asyringe under argon. The reaction mixture was heated to 40° C. andstirred for 40 min˜1 hour. Then, the reaction mixture was heated to80˜100° C. and refluxed for 72˜96 hours. The mixture was cooled to roomtemperature and the insoluble precipitated polymer was filtered andwashed with dichloromethane, methanol, water, and acetone in men.Further purification of the polymer was carried out by Soxhletextraction with methanol and dichloromethane (volume ratio=1:1) for24˜36 hours. The product CMP-2 was dried in vacuum for 24 hours at 70°C.

3) Synthesis of CMP-3:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Zn, alkynyl benzene A(mole ratio of Salen-Zn and alkynyl benzene A=1:1˜3), copper (I) iodideand tetrakis-(triphenylphosphine)palladium(0) via a syringe under argon.The reaction mixture was heated to 40° C. and stirred for 40 min˜1 hour.Then, the reaction mixture was heated to 80˜100° C. and refluxed for72˜96 hours. The mixture was cooled to room temperature and theinsoluble precipitated polymer was filtered and washed withdichloromethane, methanol, water, and acetone, in turn. Furtherpurification of the polymer was carried out by Soxhlet extraction withmethanol and dichloromethane (volume ratio=1:1) for 24˜36 hours. Theproduct CMP-3 was dried in vacuum for 24 hours at 70° C.

4) Synthesis of CMP-4:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Cu, alkynyl benzene A(mole ratio of Salen-Cu and alkynyl benzene A=1:1˜3), copper (I) iodideand tetrakis-(triphenylphosphine)palladium(0) via a syringe under argon.The reaction mixture was heated to 40° C. and stirred for 40 min˜1 hourunder an argon atmosphere. Then, the reaction mixture was heated to80˜100° C. and refluxed for 72˜96 hours. The mixture was cooled to roomtemperature and the insoluble precipitated polymer was filtered andwashed with dichloromethane, methanol, water, and acetone in turn.Further purification of the polymer was carried out by Soxhletextraction with methanol and dichloromethane (volume ratio=1:1) for24˜36 hours. The product CMP-4 was dried in vacuum for 24 hours at 70°C.

4. Synthesis of CMP-5:

The coordination reaction of the polymer with aluminum was carried outafter the polymer was obtained.

1) Synthesis of Salen:

With monohydric alcohol (methanol or ethanol) as a solvent, a mixturesolution of R₁-substituted salicylaldehyde and 1,2-diaminocyclohexane(mole ratio=1:1˜30) was stirred for 1˜15 hours at 0˜150° C. to affordthe Salen compounds;

2) Synthesis of Conjugated Microporous Polymer (CMP):

With tetrakis-(triphenylphosphine)palladium(0) and copper(I) iodide ascatalysts, salen and 1,3,5-triethynylbenzene were mixed with a moleratio of 1:1˜5. The reaction mixture was heated to 20˜150° C. andstirred for 60˜90 hours, yielding the polymer. The mole ratio of thetetrakis-(triphenylphosphine)palladium(0) and 1,3,5-triethynylbenzenewas 1:2˜50, whereas the mole ratio of copper(I) iodide and1,3,5-triethynylbenzene was 1:10˜40.

3) Synthesis of Aluminum Coordination Catalyst (CMP-5):

The aluminum compound was mixed with the CMP obtained got by theprocedure above with a quality ratio of 1:1˜6. Then the mixture reactedat 90˜130° C. for 8˜15 hours, yielding the target CMP-5.

4) Catalyzing the Coupling Reaction of CO₂ and Epoxides:

Before sufficient CO₂ was introduced, the amine compounds were added toa mixture of the CMP-Al and epoxides in which the mole ratio of theCMP-Al and epoxides was 1:1˜25, while the mole ratio of the aminecompounds and the epoxides was 1:5˜1000. Then the reaction was stirredfor 1˜80 hours at 0˜160° C., affording the cyclic carbonates. The aminecompounds mentioned above are quaternary ammonium salts, triethylamineor 4-dimethylamino pyridine.

The structures of the conjugated microporous polymer (CMP) catalysts:

wherein, R₁=—H, -^(t)Bu, -^(i)Bu, —NO₂, —Cl, —CH₂NEt₂, —CH₂N(Bn)Et₂Br,—CH₂N(CH₃)₂CH₂Ph,

X=—OAc or —Cl or —Br or —I or -Et or —OMe or —OEt or—OCH₂CH₂(OCH₂CH)₂Cl. Degree of polymerization for synthesized conjugatedpolymer compound is in the range of 30˜100. These stereochemicalstructures of the polymer catalysts are consisting of three-dimensionalcrosslinking networks. The chemical conversion of CO₂ with terminalepoxides to form corresponding cyclic carbonates under the CMP-1˜5polymer catalyst system above was achieved in excellent yields (35˜90%)of corresponding cyclic carbonate at mild conditions. And the catalystcould be reused without reducing the yields. Simultaneously, holding thereaction condition in the range of 50˜180° C. for the reactiontemperature and 2˜8 MPa for the pressure of CO₂, the yields can be up to90% above while the reaction time only takes 1˜3 hours (excluding theCMP-4).

To prepare CMP-1˜5, the dibromo-functionalized precursor monomersSalen-Co, Salen-Cr—Cl, Salen-Zn, Salen-Cu were first synthesized bycomplexation reaction of metal salt [Co(OAc)₂, CrCl₂, Et₂Zn, Cu(OAc)₂]and Salen. The resulted precursors were polymerized with alkynyl benzene(A) to produce corresponding conjugated microporous polymers (excludingthe CMP-5). The polymers generated by the procedure can adsorb CO₂molecules, increasing the solubility of CO₂ in solvent, which leads tothe improvement of the reaction yields with recycling ability.Simultaneously, the catalysts can obviously shorten the reaction timefor catalyzing the reaction of CO₂ and epoxides at high temperatures andhigh pressures.

Synthetic Routes for the Polymers (CMP-1, CMP-2, CMP-3, CMP-4):

Synthetic Routes for CMP-5:

The coupling of epoxides and CO₂ by polymer catalyst (CMP):

CMP: CMP-1, CMP-2, CMP-3, CMP-4 or CMP-5; Co-catalyst: quaternaryammonium salts (Tetrabutyl ammonium bromide and tetrabutyl ammoniumchloride and tetrabutyl ammonium acetate), TEA, DMAP; R₂=-Me, —C₂H₅,-Ph, —CH₂Ph, -Bu or —C₈H₁₇. The amount of substance ratio for epoxides,CMP and Co-catalyst is about 200˜2000:1:1.

In this invention, a series of new metal-conjugated microporous polymercatalysts were synthesized and used to catalyze the reaction of epoxidesand CO₂ to produce corresponding cyclic carbonates at ambient pressuresand temperatures. The procedure is a breakthrough for overcoming thelimitation of this reaction which can only occur at high pressure of CO₂and temperature catalyzed by other catalysts. The yields of cycliccarbonates were in the range of 30˜90% at ambient pressures andtemperatures. Remarkably, the polymer catalyst can be reused for manytimes without reducing the yields. Besides, elevating the pressure andthe temperature can shorten the reaction time to 1˜6 hours, with theyields above 90%.

BRIEF DESCRIPTION OF THE DRAWINGS

Description of the figures is provided below:

FIG. 1: ¹H NMR of the Salen[N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane as anexample] (CDCl₃, 400 MHz);

FIG. 2: ¹H NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 3: ¹³C NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 4: ¹H NMR of the 4-Choloro-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 5: ¹³C NMR of the 4-Choloro-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 6: ¹H NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 7: ¹³C NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 8: ¹H NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz z);

FIG. 9: ¹³C NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 10. ¹H NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 11: ¹³C NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl₃, 400 MHz);

FIG. 12: The FT-IR spectra of CMP-1-1;

FIG. 13: The FT-IR spectra of CMP-1-2;

FIG. 14: The FT-IR spectra of CMP-2-1;

FIG. 15: The FT-IR spectra of CMP-3-1;

FIG. 16: Solid-state NMR spectra for the CMP-5-1;

FIG. 17: Solid-state NMR spectra for the CMP-1-1;

FIG. 18: Solid-state NMR spectra for the CMP-1-2;

FIG. 19: Solid-state NMR spectra for the CMP-2-1;

FIG. 20: Solid-state NMR spectra for the CMP-3-1;

FIG. 21: Solid-state NMR spectra for the CMP-4-1.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

The technological invention embodiment is not limited in the specificexamples below, including the any combination of these detailedimplementation programs.

Example 1

1. Synthesis of Salen-Co:

A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10 ml) was added to a solutionof the Salen (0.75 mmol) in 10 mL anhydrous toluene (10 ml) via asyringe. The reaction mixture was refluxed for 5 hours at 80° C.,yielding the target Salen-Co;

2. Synthesis of Salen-Co—OAc:

The acetic acid (6.5 mmol) was added to a solution of the Salen-Co (0.65mmol) in toluene (6 ml) and CH₂Cl₂ (18 ml) via a syringe under argon.The mixture was stirred for 5 hours at 25° C., yielding the targetSalen-Co—OAc, and its NMR spectrum was shown in FIG. 2.

3. Synthesis of CMP-1-1:

Salen-Co—OAc (0.45 mmol), 1,3,5-triethynylbenzene (1.35 mmol), copper(I)iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg)were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml).Then the reaction mixture was refluxed at 85° C. for 72 hours. Afterpost-processing, CMP-1-1 was obtained. The FT-IR spectra and theSolid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG.17, respectively.

4. Catalyzing for the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours at ambient pressure and temperature, and theyield of the propylene carbonate is 87.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 6 hours at 45° C., and theyield of the propylene carbonate is 94.5%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4.

Example 2

1. Synthesis of Salen-Co:

A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10 ml) was added to a solutionof the Salen (0.6 mmol) anhydrous toluene (10 ml) via a syringe. Thenthe reaction mixture was refluxed for 5 hours at 80° C., yielding thetarget Salen-Co;

2. Synthesis of Salen-Co—OAc:

The acetic acid (5 mmol) was added to a solution of the Salen-Co (0.5mmol) in toluene (5 ml) and CH₂Cl₂ (15 ml) via a syringe under argon.Then the mixture was stirred for 5 hours at 25° C., yielding the targetSalen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

3. Synthesis of CMP-1-1:

Salen-Co—OAc (0.6 mmol), 1,3,5-triethynylbenzene (2.4 mmol), copper(I)iodide (60 mg) and tetrakis-(triphenylphosphine)palladium(0) (100 mg)were dissolved in a mixture of toluene (16 ml) and triethylamine (6 ml).Then the reaction mixture was refluxed at 85° C. for 72 hours. Afterpost-processing, CMP-1-1 was obtained. The FT-IR spectra and theSolid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG.17, respectively.

4. Catalyzing the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-1-1, 400 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours at ambient pressure and temperature, and theyield of the propylene carbonate is 80.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 4 hours at 60° C., and theyield of the propylene carbonate is 98.5%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4;

3) A mixture of 100 mg CMP-1-1, 200 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at the ambient pressure and temperature,and the yield of the propylene carbonate is 56.5%;

4) With 5.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 12 hours at 30° C., and theyield of the propylene carbonate is 94.0%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4.

Example 3

1. Synthesis of Salen-Co:

A solution of Co(OAc)₂ (1 mmol) in CH₃OH (8 ml) was added to a solutionof the Salen (0.5 mmol) in 8 mL anhydrous toluene (10 ml) via a syringe.The reaction mixture was refluxed for 5 hours at 80° C., yielding thetarget Salen-Co;

2. Synthesis of Salen-Co—OAc:

The acetic acid (9 mmol) was added to a solution of Salen-Co (0.65 mmol)in toluene (5 ml) and CH₂Cl₂ (15 ml) via a syringe under argon. Themixture was stirred for 6 hours at 25° C., yielding the targetSalen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

3. Synthesis of CMP-1-1:

Salen-Co—OAc (0.6 mmol), 1,3,5-triethynylbenzene (2.0 mmol), copper(I)iodide (50 mg) and tetrakis-(triphenylphosphine)palladium(0) (100 mg)were dissolved in a mixture of toluene (16 ml) and triethylamine (5 ml).Then the reaction mixture was refluxed at 85° C. for 72 hours. Afterpost-processing, CMP-1-1 was obtained. The FT-IR spectra and theSolid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG. 17respectively.

4. Catalyzing the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-1, 400 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 96.5%;2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 3 hours at 70° C., and theyield of the propylene carbonate is 97%;3) A mixture of 100 mg CMP-1, 200 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at the ambient pressure and temperature,and the yield of the propylene carbonate is 66.5%;4) With 5.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 12 hours at 30° C., and theyield of the propylene carbonate is 94.0%;5) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 60 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 91.5%;6) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 36 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 76.5%.

Example 4

1. Synthesis of Salen-Co:

A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10 ml) was added to a solutionof the Salen (0.6 mmol) in 10 ml anhydrous toluene via a syringe. Thereaction mixture was refluxed for 5 hours at 80° C., yielding the targetSalen-Co.

2. Synthesis of Salen-Co—OAc:

The acetic acid (5 mmol) was added to a solution of the Salen-Co (0.5mmol) in toluene (5 ml) and CH₂Cl₂ (15 ml) via a syringe under argon.The mixture was stirred for 5 hours at 25° C., yielding the targetSalen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

3. Synthesis of CMP-1-2:

Salen-Co—OAc (0.6 mmol), 1,4-diacetylenebenzene (1.2 mmol), copper(I)iodide (50 mg) and tetrakis-(triphenylphosphine)palladium(0) (90 mg)were dissolved in a mixture of toluene (16 ml) and triethylamine (6 ml).Then the reaction mixture was refluxed at 85° C. for 72 hours. Afterpost-processing, CMP-1-2 was obtained. The FT-IR spectra and theSolid-state NMR spectra of the CMP-1-2 were shown in FIG. 13 and FIG.18, respectively.

4. Catalyzing for the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 66.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 90° C., and theyield of the propylene carbonate is 85.9%;

3) With 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide in themixture, the reaction mixture was stirred for 24 hours in CO₂ at ambientpressure and temperature, and the yield of the propylene carbonate is52.5%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 110° C., and theyield of the propylene carbonate is 91.1%;

5) With 4.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 120° C., and theyield of the propylene carbonate is 64.2%. The ¹H and ¹³C NMR spectrumsfor the propylene carbonate were shown in FIG. 3 and FIG. 4.

Example 5

1. Synthesis of Salen-Cr—Cl:

The chromium (II) chloride (0.8 mmol) and Salen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.6mmol) were dissolved in dried THF (12 mL). The mixture was stirred underargon at 25° C. for 24 hours and for another 24 hours in the air. Afterthat the compound Salen-Cr—Cl was obtained.

2. Synthesis of CMP-2:

1) Synthesis of CMP-2-1: Salen-Cr—Cl (0.4 mmol), 1,3,5-triethynylbenzene(1.2 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-2-1. The FT-IR spectra and the Solid-state NMR spectra ofthe CMP-2-1 were shown in FIG. 14 and FIG. 19, respectively;

2) Synthesis of CMP-2-2: Salen-Cr—Cl (0.45 mmol), 1,4-diethynylbenzene(1.35 mmol), copper(I) iodide (30 mg) andtetrakis-(triphenylphosphine)palladium(0) (60 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-2-2;

3) Synthesis of CMP-2-3: Salen-Cr—Cl (0.4 mmol),tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-2-3.

3. Catalyzing for the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-2-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 67.7%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and theyield of the propylene carbonate is 98.5%. The NMR spectrums for theproduct were shown in FIG. 2 and FIG. 3;

3) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 1.96 ml epichlorohydrin was stirred for 1 hour at 100° C., and theyield of the corresponding cyclic carbonate is 99.1%. The NMR spectrumsfor the product were shown in FIG. 4 and FIG. 5;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.0%. The NMR spectrumsfor the product were shown in FIG. 6 and FIG. 7;

5) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.7%. The NMR spectrumsfor the product were shown in FIG. 8 and FIG. 9;

6) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.3%. The NMR spectrumsfor the product were shown in FIG. 10 and FIG. 1;

7) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 86.5%.

Example 6

1. Synthesis of Salen-Zn:

The Et₂Zn (0.4 ml, 1.0 M in hexane) and Salen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.4mmol) and were dissolved in dried THF (20 ml). The mixture was stirredunder argon at 25° C. for 24 hours. After that the compound Salen-Zn wasobtained.

2. Synthesis of CMP-3:

1) Synthesis of CMP-3-1: Salen-Zn (0.35 mmol), 1,3,5-triethynylbenzene(1.05 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-1. The FT-IR spectra and the Solid-state NMR spectra ofthe CMP-3-1 were shown in FIG. 15 and FIG. 20, respectively.

2) Synthesis of CMP-3-2: Salen-Zn (0.4 mmol), 1,4-diethynylbenzene (1.2mmol), copper(I) iodide (35 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-2.

3) Synthesis of CMP-3-3: Salen-Zn (0.4 mmol),tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-3.

3. Catalyzing the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-3-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred 48 hours in CO₂ at ambient pressure and temperature, and theyield of the propylene carbonate is 85.1%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the propylene carbonate is 95.2%;

3) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 1.96 ml epichlorohydrin was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 99.6%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.5%;

5) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 98.3%;

6) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.6%;

7) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and theyield of the corresponding cyclic carbonate is 88.7%.

Example 7

1. Synthesis of Salen-Cu:

The Cu(OAc)₂ (0.5 mmol) and Salen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane, 0.5mmol) and were dissolved in dried ethanol (20 mL). The mixture wasstirred at 80° C. for 24 hours. After that the compound Salen-Cu wasobtained.

2. Synthesis of CMP-4:

1) Synthesis of CMP-4-1: Salen-Cu (0.46 mmol), 1,3,5-triethynylbenzene(1.32 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-4-1. The Solid-state NMR spectra of the CMP-4-1 were shownin FIG. 21.

2) Synthesis of CMP-4-2: Salen-Cu (0.4 mmol), 1,4-diethynylbenzene (1.2mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-4-2.

3) Synthesis of CMP-4-3: Salen-Cu (0.45 mmol),tetrakis(4-ethynylphenyl)methane (1.35 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-4-3.

3. Catalyzing for the Coupling Reaction of CO₂ and Epoxides:

1) A mixture of 100 mg CMP-4-1, 400 mg TBAB and 1.75 ml propylene oxidewas stirred for 72 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 58.5%;

2) A mixture of 100 mg CMP-4-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 51.3%;

3) A mixture of 100 mg CMP-4-1, 200 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 42.7%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-4-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the propylene carbonate is 52.7%.

Example 8

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofsalicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) wasstirred at 40° C. for 5 hours, yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlEt₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 2 hours, the yield of the propylene carbonateis 30%.

Example 9

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofsalicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) wasstirred at 40° C. for 5 hours, yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlCl₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 39.8%.

Example 10

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with propanol as solvent, a mixture of^(t)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 50° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlBr₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 10 hours, the yield of the propylene carbonateis 52.1%.

Example 11

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofCl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlEt₃ (20 mg) was stirred and refluxedat 140° C. for 8 hours, yielding the target catalyst CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 20 hours, the yield of the propylene carbonateis 63.4%.

Example 12

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofCl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlCl₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 10° C. for 6 hours, the yield of the propylene carbonateis 40.3%.

Example 13

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofNO₂-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 50° C. for 10 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (100 mg) and AlEt₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 53.5%.

Example 14

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with i-propanol as solvent, a mixture of^(i)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (100 mg) and AlBr₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 15° C. for 20 hours, the yield of the propylene carbonateis 83.7%.

Example 15

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and Epoxides:

1) Synthesis of Salen: with i-propanol as solvent, a mixture of^(i)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OEt)₃ (20 mg) was stirred andrefluxed at 90° C. for 8 hours, yielding the target catalyst CMP-5-1.

4) Catalyzation for the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:10)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 68.2%.

Example 16

Synthesis of CMP-5-1 and its Catalyzation for the Coupling Reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with hexanol as solvent, a mixture ofCH₂N(CH₃)₂CH₂Ph-substituted salicylaldehyde (6.0 mmol) and1,2-diaminocyclohexane (7.0 mmol) was stirred at 80° C. for 5 hours,yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OMe)₃ (20 mg) was stirred andrefluxed at 90° C. for 8 hours, yielding the target catalyst compoundCMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 13 hours, the yield of the propylene carbonateis 89.6%.

Example 17

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with butanol as solvent, a mixture ofCH₂N(Bn)Et₂Br-substituted salicylaldehyde (6.0 mmol) and1,2-diaminocyclohexane (7.0 mmol) was stirred at 25° C. for hours,yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OMe)₃ (20 mg) was stirred andrefluxed at 100° C. for hours, yielding the target catalyst CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5),was stirred at 0° C. for 20 hours, the yield of the propylene carbonateis 93.5%.

Using the polymers as catalysts to catalyze the coupling reaction of CO2and epoxides, the yields of the cyclic carbonates were in the range of35˜90%. The catalysts can be reused for several times without reducingthe yields which can reach to 90% above at high pressure (2˜8 MPa) andthe temperature of 50˜120° C. for 1˜3 hours. The procedure is abreakthrough for overcoming the limitation of this reaction which canonly occur at high pressure and temperature catalyzed by othercatalysts. Meanwhile the reuse of the catalysts can figure out thetroubles caused by the low efficiency of the other catalysts.

1. A cobalt, chromium, zinc, copper or aluminum-conjugated microporouspolymer catalyst (CMP) having one of the following structures: 1) CMP-1,a cobalt-conjugated microporous polymer: the structures of CMP-1-1:

the structures of CMP-1-2:

the structures of CMP-1-3:

2) CMP-2, a chromium-conjugated microporous polymer: the structures ofCMP-2-1:

the structures of CMP-2-2:

the structures of CMP-2-3:

3) CMP-3, a zinc-conjugated microporous polymer; the structures ofCMP-3-1:

the structures of CMP-3-2:

the structures of CMP-3-3:

4) CMP-4, a copper-conjugated microporous polymer: the structures ofCMP-4-1:

the structures of CMP-4-2:

the structures of CMP-4-3:

5) CMP-5, an aluminum-conjugated microporous polymer: the structures ofCMP-5-1:

the structures of CMP-5-2:

the structures of CMP-5-3:

wherein, R₁=—H, -^(t)Bu, ^(i)Bu, —NO₂, —Cl, —CH₂NEt₂, —CH₂N(Bn)Et₂Br,—CH₂N(CH₃)₂CH₂Ph,

X=—OAc or —Cl or —Br or —I or -Et or —OMe or —OEt or—OCH₂CH₂(OCH₂CH)₂Cl, and the degree of polymerization for thesynthesized conjugated polymer compound is in the range of 30˜100.
 2. Amethod for preparing the polymer catalyst CMP of claim 1 (except forCMP-A1) comprising: 1) synthesis of Salen: with the methanol or ethanolas a solvent, a mixture solution of R₁-substituted salicylaldehyde and1,2-diaminocyclohexane (mole ratio=1:1˜30) was stirred for 3˜15 hours at0˜150° C., affording the Salen compounds; 2) synthesis of Salen-Co: withthe toluene and ethanol as solvent (volume ratio=1:1), a mixturesolution of Co(OAc)₂ and Salen (mole ratio=1.52:1) was stirred underargon for 4˜6 hours at 80˜100° C., affording the Salen-Co compounds; 3)synthesis of Salen-Co—X: with the anhydrous toluene and CH₂Cl₂ assolvent (volume ratio=1:3), a mixture solution of Salen-Co andCH₃COOH(HCl or HBr) (mole ratio=1:10˜15) was stirred under argon for 5˜7hours at 25° C., affording the Salen-Co—X compounds; 4) synthesis ofSalen-Cr—Cl: with the anhydrous THF as a solvent, a mixture solution ofCrCl₂ and Salen (mole ratio=1:0.6˜0.75) was stirred under argon for16˜24 hours at 25° C., then continue stirring 16˜24 hours in atmosphere,affording the Salen-Cr—Cl compounds; 5) synthesis of Salen-Zn: with theanhydrous THF as a solvent, a mixture solution of Et₂Zn and Salen (moleratio=1:0.8˜1) was stirred under argon for 20˜24 hours at 25° C.,affording the Salen-Zn compounds; 6) synthesis of Salen-Cu: with theanhydrous ethanol as a solvent, a mixture solution of anhydrous Cu(OAc)₂and Salen (mole ratio=1:0.9˜1) was stirred under argon for 16˜24 hoursat 80˜90° C., affording the Salen-Cu compounds; 7) synthesis ofconjugated microporous polymer (CMP): with the anhydrous toluene and TEAas solvent (volume ratio=3˜4:1), CuI andtetrakis-(triphenylphosphine)palladium(0) as catalyst, a mixturesolution of alkynyl benzene A and Salen-Co—OAc, Salen-Cr—Cl, Salen-Zn orSalen-Cu (mole ratio=1˜4:1) was stirred under argon for 60˜90 hours at25˜100° C., affording the CMP compounds. The mole ratio of CuI ortetrakis-(triphenylphosphine)palladium(0) and alkynyl benzene A was1:5˜10 and 1:20˜30, respectively.
 3. A method for preparing the polymercatalyst CMP-Al of claim 1 comprising: 1) synthesis of Salen: WithMonohydric alcohol (methanol or ethanol) as a solvent, a mixturesolution of R₁-substituted salicylaldehyde and 1,2-diaminocyclohexane(mole ratio=1:1˜30) was stirred for 1˜15 hours at 0˜150° C., affordingthe Salen compounds. Wherein, R₁=—H, -^(t)Bu, ^(i)Bu, —NO₂, —Cl,—CH₂NEt₂, —CH₂N(Bn)Et₂Br, —CH₂N(CH₃)₂CH₂Ph,

2) synthesis of conjugated microporous polymer (CMP): with the anhydroustoluene and TEA as solvent (volume ratio=3˜4:1),tetrakis-(triphenylphosphine)palladium(0) and CuI as catalyst, a mixturesolution of alkynyl benzene A and Salen (mole ratio=1:1˜5) was stirredunder argon for 60˜90 hours at 20˜150° C., affording the CMP compounds.Wherein, the mole ratio of CuI ortetrakis-(triphenylphosphine)palladium(0) and alkynyl benzene A was1:10˜40 and 1:1˜250, respectively; 3) synthesis of aluminum-conjugatedmicroporous polymer catalyst (CMP-Al): with the anhydrous toluene assolvent, a mixture solution of aluminum compound and CMP (massratio=1:1˜6) was stirred for 8˜15 hours at 90˜130° C., affording theCMP-Al catalyst. Wherein, the structures of the aluminum compounds wereAlCl₃, AlBr₃, AlEt₃, Al(OMe)₃, Al(OEt)₃ or Al(OCH₂CH₂(OCH₂CH)₂Cl)₃. 4.The method of claim 2 wherein: 1) the amount of andydrous ethanolrequired by each 1 mmol 1,2-diaminocyclohexane is 15˜20 ml; 2) theamount of toluene required by each 1 mmol Salen is 12˜20 ml; 3) theamount of toluene required by each 1 mmol Salen-Co is 8˜16 ml; 4) theamount of anhydrous THF required by each 1 mmol Salen is 15˜20 ml; 5)the amount of anhydrous ethanol required by each 1 mmol Salen is 30˜45ml; 6) the amount of anhydrous toluene required by each 1 mmolSalen-Co—X, Salen-Cr—Cl, Salen-Zn or Salen-Cu is 30˜50 ml.
 5. The methodof claim 3 wherein: 1) monohydric alcohol was monohydric aliphaticalcohol in step 1); stirred for 2˜10 hours at 30˜120° C., afforded theSalen compounds. Wherein, monohydric aliphatic alcohol was methanol,ethanol, propanol, butanol, isopropyl alcohol or hexyl alcohol; 2) Themole ratio of substituted salicylaldehyde and 1,2-diaminocyclohexane instep 1) was 1:1˜20; 3) The mole ratio of substituted salicylaldehyde and1,2-diaminocyclohexane in step 1) was 1:1˜6; 4) The mole ratio of1,3,5-triethynylbenzene and Salen in step 2) was 1:1˜3; the mole ratioof tetrakis-(triphenylphosphine)palladium(0) or CuI and1,3,5-triethynylbenzene in step 2) was 1:12˜28, 1:10˜25, respectively;5) The mass ratio of aluminum compound and CMP in step 3) was 1:1˜2.5,afforded conjugated microporous polymer catalyst CMP-Al.
 6. The methodof claim 3 wherein: 1) the amount of anhydrous toluene required by each1 mmol Salen is 20˜25 ml; 2) the amount of anhydrous toluene required byeach 1 g polymer is 15˜20 ml.
 7. The method of claim 2, wherein: thealkynyl benzene A was 1,3,5-triethynylbenzene, 1,4-diethynylbenzene ortetrakis(4-ethynylphenyl) methane.
 8. An application for catalysts ofclaim 1, wherein: all the polymer catalysts can be used to catalyze thereaction of CO₂ and epoxides at 0˜180° C. and 0.1˜8.0 MPa CO₂ pressure.9. The application of claim 8, wherein: 1) general procedure for thecatalytic reaction of CO₂ and epoxides at ambient pressure andtemperature: In the present of a certain amount of amine compounds, amixture solution of CMP (except CMP-Al) and epoxides (massratio=1:10˜50) was stirred for 12˜72 hours at ambient pressure andtemperature, afforded the corresponding cyclic carbonates. Wherein, themole ratio of amine compounds and epoxides in step was 1:10˜100; 2)general procedure for the catalytic reaction of CO₂ and epoxides at hightemperatures and pressures: In the present of a certain amount of aminecompounds, a mixture solution of CMP (except CMP-Al) and epoxides (massratio=1:10˜50) was stirred for 1˜6 hours at 50˜160° C. and 2˜8 MPa CO₂pressure, afforded the corresponding cyclic carbonates. wherein, themole ratio of amine compounds and epoxides was 1:10˜100.
 10. Theapplication of claim 8, wherein: general procedure for using the CMP-Alto catalyze reaction of CO₂ and epoxides: In the present of a certainamount of amine compounds, a mixture solution of CMP-Al and epoxides(mass ratio of CMP-Al and epoxides=1:1˜25) was stirred for 3˜80 hours at0˜160° C. and appropriate CO₂ pressure, afforded the correspondingcyclic carbonates. Wherein, the mole ratio of amine compounds andepoxides was 1:5˜1000.
 11. The application of claim 10, wherein, themole ratio of amine compounds and epoxides was 1:900.
 12. Theapplication of claim 9, wherein, the amine compounds were quaternaryammonium salt (tetrabutyl ammonium chloride, tetrabutyl ammoniumbromide, tetrabutyl ammonium iodide or tetrabutyl ammonium acetate),triethylamine (TEA) or dimethylaminopyridine (DMAP).
 13. The applicationof claim 9, wherein, the epoxides were propylene oxide, epichlorohydrin,2-ethyloxirane, 2-butyloxirane or 2-phenyloxirane.
 14. The method ofclaim 3, wherein: the alkynyl benzene A is 1,3,5-triethynylbenzene,1,4-diethynylbenzene or tetrakis(4-ethynylphenyl) methane.
 15. Theapplication of claim 10, wherein, the amine compounds are quaternaryammonium salt (tetrabutyl ammonium chloride, tetrabutyl ammoniumbromide, tetrabutyl ammonium iodide or tetrabutyl ammonium acetate),triethylamine (TEA) or dimethylaminopyridine (DMAP).
 16. The applicationof claim 10, wherein, the epoxides are propylene oxide, epichlorohydrin,2-ethyloxirane, 2-butyloxirane or 2-phenyloxirane.